Bis(4-beta-hydroxyalkoxyphenyl) ketones and process of preparation



Patented Apr. 13, 1954 UNITED STATES PATENT OFF-I CE BIS (4 p HYDROXYALKOXYPHENYL) KETONES AND PROCESS OF IKEP- ArtATiON John R. Caldwell, Kingsport, Tenn., assignor to Eastman KOOaK Company, hocnester, N. 36., a corporation or New Jersey No Drawing. Original application April 11, 1951,

Serial No. 225M150. Divided and this application November :46, 195K, penal no. 5556,1500

6 Claims. (Cl. 260-591) wherein R represents an allsyndene or cycloalkylldene radical (U. S. Patent 2,331,265 issued October 5, 1943) to form his (4-p-hydroxyalkoxyphenyl) compounds. This patent also discloses the esterliication of these hydroxyalkoxy compounds with monobasic carboxylic acids; however, the products obtained are principally useful only as plasticizing agents for other resins because of their generally low melting or softening points. Thus, in Example 1 of the above patent, 2,2-di(4 [3 hydroxyethoxyphenyl) propane, is disclosed and is said to melt at approximately 112 C. In contrast, the products of my invention (wherein there is a ketone group in place of the alkylidene or cycloalkylidene group) possess greatly increased melting points, e. g., the substitution of the CO- group for the 2,2-propylidene group in the above mentioned compound described in Example 1 of the patent referred to, results in a product which melts at 173 C. which is an increase of 61 C. This is a very high melting point for a compound containing two ether linkages and is not believed to have been predictable from the characteristics of analogous known compounds.

Other prior art patents disclosing products and processes of interest include U. S. 2,324,483, dated Jul 20, 1943, and U. S. 2,444,333, dated June 29, 1948. According to these patents chlorohydrins are employed instead of ethylene oxide and the products obtained do not have a keto group separating the phenylene groups.

According to my invention, I have found that his (4-5 hydroxyalkoxyphenyl) ketones having the general formula:

wherein R represents an alkylene radical and X represents one or more substituents selected from hydrogen atoms and/or lower alkyl radicals located in either the ortho or meta positions, can be prepared by reacting, in the presence of a 2' catalyst, a his l-hydroxyphenyl) ketone having the general lormula;

x C) u 'c- CD -OH (X having been uenned above) with an alkylene oxide wherein the epoxy lmsage connects adiacent carbon atoms. rurthermore, l have also found that these bis kl-p-nyoroxyalkoxyphenyl) ketones iorm polyesters upon being reacted wlth polybasic carboxync acids.

By "alsylene radical," as employed herein, I mean a divalent radical where rt in the above formula has the formula:

wherein each of R1 and R2 represents a hydrogen atom or a low molecular weight alkyl radical such as a methyl or an ethyl radical, Thus, I specifically intend to include the radicals which comes within the scope of my expression alkylene radical containing lrom 2 to 4 carbon atoms as employed hcrelnaiter.

It is an ODJBCD or my invention to provide new and useiul compounds, ViZ. bis l4-p-hyoroxyalkoxyphenyl) Ketones, and. a process ior their preparatlon. It is also an object of my invention to provide a new series of valuable polyesters 01' my new bis l4-p-nydroxyallsoxyphenyll ketones, especially his i l-p-hydroxyethoxypnenyl) ketone, with polybaslc (particularly dlbasic) acids and a process for their manuiacture. Other objects will become apparent hereinafter.

The polyesters produced in accordance with my invention are valuable in the manufacture of fibers, threads, sheets, films, coating compositions, molding compositions, etc. These polyesters are characterized by their hardness and high melting point. One of the most important uses of these polyesters is in the field of protective coatings. These polyesters impart a high degree of surface hardness and moisture resistance when incorporated in various types of air drying and baking enamels, varnishes and lacquers,

In accordance with my invention I can react, in the presence of a catalyst, one or more bis (4-hydroxyphenyl) ketones having the formula:

wherein R represents an alkylene radical containing from 2 to 4 carbon atoms.

The bis (4-hydroxyphenyl) ketone which is employed can be readily prepared by known methods from phenol and phosgene. tively, as indicated in the first general formula of this specification, I can also employ nuclearly substituted bis (4-hydroxyphenyl) ketones in ac= cordance with my invention. Such ketones can be prepared by reacting nuclearly substituted phenols with phosgene. Thus bis (4-hydroxy-3- methylplienyl) ketone can be prepared by heating o-cresol with phosgene. Likewise, bis (4=hydroxy-Z-methylphenyl) ketone can be similarly prepared by employing m-cresol. Similarly, other analogous compoundscan be prepared by reacting other nuclearly substituted phenols, e. g., m-ethylphenol, o-ethylphenol, etc. with phosgene to produce bis (4-hydroxy-3-ethylphenyl) ketone, bis l-hydroxy-Z-ethylphenyl) ketone, etc.

The alkylene oxides which I can advantageously Alternaemploy include ethylene oxide, 1,2-propylene V oxide, 1,2-butylene oxide and 2,3-butylene oxide. Most advantageously, I employ ethylene oxide. From 2 to 3 mols of the alkylene oxide are advantageously employed per mol of the bis (i-hydroxyphenyl) ketone. Larger and smaller ratios can also be employed; however, most advantageously, a range of from 2.2 to 2.4 mols of the alkylene oxide per mol of the ketone is employed.

I It is advantageous to conduct the reaction in the presenceof a catalyst. Advantageously, alkaline type catalysts such as the alkali metal hydroxides, alkoxides'or alcoholates, and the quaternary ammonium hydroxides can be employed. Examples of such catalysts include sodium hydroxide, potassium propoxide, sodium ethoxide, potassium methoxide, potassium hydroxide, tetramethyl ammonium hydroxide, trimethylbenzyl ammonium hydroxide, etc. The proportion of catalyst advantageously employed varies from about 0.1 to about 2% by weight of the his (4- hydroxyphenyl) ketone being reacted. However, higher or lower percentages can also be employed. It is also possible to employ other alkaline catalysts than those specifically mentioned above, e. g., the alkaline earth alkoxides, alcoholates, etc.

In carrying out the reaction it is advantageous to employ an unreactive solvent (viz. an inert solvent) which does not enter into the reaction itself. Solvents such as the lower aliphatic alcohole are most advantageously employed, e. g., methyl alcohol, ethyl alcohol, isopropyl alcohol, etc. However, other well known solvents may also be employed with advantage, e. g., dioxane, methoxyethyl alcohol, tetrahydrofuran, etc.

The reactants, catalyst and solvent can be placed in the reaction vessel in any desired sequence or simultaneously. Advantageously, the ethylene oxide can be introduced into a vessel containing the other materials, during the course of the reaction. The reaction can be advantageously conducted in a closed vessel under autogenous pressures.

Advantageously, I carry out the reaction at a temperature of from about 80 to about 140 C.

4 Most advantageously I employ temperatures in the range of from to C.

Upon completion of the reaction' the product can be readily purified by stirring with an aqueous dilute alkaline solutinon of KOI-I, NaOH, etc. to .remove the unreacted bis l-hydroxyphenyl) ketone by dissolution thereof. The product can then be separated by filtration and recrystallized from a suitable solvent such as methyl alcohol, a mixture of benzene and ethyl alcohol, etc. Other methods of purification can also be used as may be expedient under any given set of circumstances, e.'g. by distillation, etc. The bis (l-,3- hydroxyalkoxyphenyl) ketones are soluble in many solvents such asdioxane, isopropyl alcohol, ethylalcohol, acetone, methyl alcohol, etc., which can be heated to facilitate the dissolution therein.

The bis (4-5-hydroxyalkoxyphenyl) ketones can be employed in the manufacture of the linear polyesters (referred to previously) by esterifying these ketones with polybasic (especially dibasic) carboxylic acids. Since the bis l-,B-hydroxyalkoxyphenyl) ketones possess unusually high melting points for their particular type of compounds (viz. diether compounds), the polyesters derived therefrom tend also to have high melting or softening points. In order to obtain polyesters possessing the highest melting or softening'points, bis l-fi-hydroxyethoxyphenyl) ketone is advantageously employed. The employment of the propylene and butylene derivatives, instead of the ethylene derivative, results in lower melting or softening points in the polyesters obtained and they are accordingly not as satisfactory for most purposes.

Advantageously, I employ dicarboxylic acids containing from 4 to 10 carbonatoms selected from among the saturated and unsaturated aliphatic acids and the monocyclic aromatic acids. It is sometimes advantageous to employ the acids as their anhydrides or lower alkyl esters; hence, when I refer to an acid or to acids, it is to be understood that the anhydrides or esters can also be employed. Examples of dicarboxylic acids which can be advantageously employed include succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic'acid, o-phthalic acid, maleic acid,

fumaric acid, itaconic acid, etc. The anhydrides and esters of these acids can also be employed in most instances with efiicacy. The wide variety of saturated and unsaturated aliphatic and aromatic dibasic acids, anhydrides and esters which can be employed in reactions with dihydric alcohols to form linear polyesters is well set forth in the prior art and most of them can be utilized in accordance with my invention. Mixed polyesters containing the dihydric bis l-flhydroxyalkoxyphenyl) ketones in combination with other dihydric and polyhydric alcohols such as the glycols, glycerine, etc. can also be prepared. In addition, oil-modified alkyd resins can be prepared by esterifying mixtures of the bis (4-phydroxyalkoxyphenyl) ketones and glycerols with phthalic acid, linseed fatty'acids, various other natural or derived acids, etc. according to known procedures. The method of esterification depends upon the nature of the particular acids and/or additive glycols, glycerols, etc. being employed.

In preparing such esters it is usually advantageous to employ a condensation agent or catalyst such as sodium hydroxide, calcium oxide, zinc chloride, sulfuric acid, toluene sulfonic acid,

etc. Other equally efficacious condensing agents I and can 'alsobe employed. It is also advantageous to employ an inert atmosphere, e. g. ni-

ss: trogen, under which to conduct the polyesteriflcation, especially when highly polymerized products are desired. Temperatures from about 125 to about 275 C. can be employed in conducting the polyesterification reaction.

The following examples will serve to illustrate further the manner of practicing my invention;

EXAMPLE 1 Bis (4-p-hydroxyethoxyphenyl) ketone 42 grams of his (4-hydroxyphenyl) ketone, 20 grams of ethylene oxide, 150 cc. of methyl alcohol, and 0.5 gram of sodium methoxide were placed in an autoclave. This mixture was stirred at a temperature of from 90 to 100 C. for six hours. The methyl alcohol was then evaporated on a steam bath and the crystalline residue was stirred at 70 to 80 C. with 200 cc. of water and 10 grams of sodium hydroxide. This mixture was cooled and filtered. The crystals which remained were washed with cold Water. The yield obtained was about 55 to 56 grams of bis (4-phydroxyethoxyphenyl) ketone which has a melting point of 170-173 0. Upon recrystallization of this material from methyl alcohol, a melting point of 174 C. was obtained and the product had an analysis of 11.0 percent hydroxyl content as compared to the theoretical percentage of 11.2 percent.

EXAMPLE 2 Bis (4-p-hydrozcyethomyphenyl) ketone 42 grams of bis (4-hydroxyphenyl) ketone, 150 cc. of ethyl alcohol, and 0.6 gram of potassium hydroxide were placed in an autoclave. The mixture was then stirred at 110 C. while 20 grams of ethylene oxide were pumped into the mixture during a period of two hours. The product obtained was isolated in the same manner as described in Example 1 above, giving a yield of from about 85 to 90 percent of bis (4-,6-hydroxyethoxyphenyl) ketone.

EXAMPLE 3 Polyester of Example 1 ketone with adipzc acid 302 grams (1.0 mol) of bis (4-fl-hydroxyethoxyphenyl) ketone (prepared in accordance with Example 1) was mixed with 146 grams (1.0 mol) adipic acid and 0.5 gram of zinc chloride was added. This mixture was melted and a stream of nitrogen bubbled through the liquid in order to provide agitation and to exclude oxygen. The temperature was maintained at 150- 160 C. for three hours. The temperature was then raised to 180-200 C. for four hours, following which the product was heated at a reduced pressure of about one to two mm. of Hg pressure at 180-200 C. for three additional hours. The product obtained was a pale yellow translucent solid. It had a melting point of from about 90 to 100 C. It is soluble in hot dioxane, hot cresol, and dimethyl acetamide. This polyestercan be pulled into fibers at the melting point. It is useful as an ingredient of varnishes, lacquers, and other protective coatings where it imparts hardness and resistance to moisture. In

order to produce such protective coatings, other resins such as phenolic resins, urea resins, and alkyd resins, can be combined with the polyester prepared in accordance with this example.

ethoxyphenyl) ketone, 258 grams (1.0 mol) of ethyl sebacate and 0.4 gram of Mg(OC-H3)z in 5 cc. of methanol were mixed together. This mixture was stirred under an atmosphere of dry nitrogen gas and heated at 170-180 C. for five hours. The temperature was then raised to 200-210 C. for two additional hours, after which the mixture was heated under a reduced pressure of about one to two mm. of Hg pressure at approximately the same temperature for an additional four hours. The polyester obtained was a hard, tough solid which had a melting point of about to C. This polyester is soluble in hot dioxane, hot acetic acid, and cresol. It can be extruded or pressed into sheets. tubes, plates, rods, etc. It is also useful as an ingredient in varnishes and other protective coatings. It is especially valuable for use as a solvent resistant gasket and packing material.

EXAMPLE 5 Polyester employing ethyl m-ph'thalate which is remarkably high for an organic ma terial; this refractive index corresponds to that of optical glass. The polyester obtained is especially valuable for the manufacture by injection molding of optical equipment. such as lenses, prisms, etc.

EXAMPLEfi Polyester employing ethyl m-phthalate and ethyl terephthalate 302 grams (1.0 mol) of his (4-p-hydroxyethoxyphenyl) ketone, 111 grams (0.5 mol) of ethyl m-phthalate (ethyl isophthalate) and 111 grams (0.5 mol) of ethyl terephthalate were mixed with 0.3 gram of potassium ethoxide. This mixture was then treated in accordance with the process set forth in Example 4. The polyester obtained had a melting point of to C. It can be spun into fibers than can be cold drawn. It has a refractive index of 1.74. The polyester is especially valuable for the manufacture of lenses and prisms by injection molding methods.

Mixed polyesters containing bis (4-p-hydroxyethoxyphenyl) ketone and other polyhydroxy compounds such as the diols, triols, etc., can be prepared in a manner similar to that set forth above. For example, a mixture of 2 parts of his (4-,3-hydroxyethoxyphenyl) ketone prepared as described in Example 2 and 1 part of ethylene glycol can be esterfied with o-phthalic acid to give a resin that results in improved surface hardness when incorporated in baking enamels.

When surface coating resins are desired, it is advantageous to employ a relatively low molecular weight polyester. To obtain such a polyester, the bis (4-5-hydroxyethoxyphenyl) ketone (prepared as in either Example 1 or 2) can be heated together with a suitable polybasic acid, ester or anhydride at a temperature of from about 150 to 200 C. for from about 3 to 6 hours until a product is obtained having a desirable acid number of, for example, from about 10 to 2D.

- complete the reaction. Of course, other low pres- What I: claim is my invention and .desire to secure by Letters Patent '01 the United States is: Lbis' '-(4-p-hydroxyethoxyphenyl) ketones having the formula:

Catalysts such as described above can be ailvantageously employed. V I

When it is desired to'produce polyesters useful in the manufacture of fibers and molding plasx x r nowixrn-cnm-O A L -o-cHR,"oH-R.o11

tics, it is advantageous'to employpolyesters havwherein R1 and R2 contain, when added together, ing higher molecular weights. In such cases, no more than two carbon atoms and X, R1 and the resins require relatively long periods of heat- R2 each represents a member of the group coning at elevated temperatures such as 200? C. sisting of a hydrogen atom, a methyl radical and or higher, and must thereafter be heated under an ethyl radical, X beinglocated in a position greatly reduced pressure in order to complete the selected from the ortho and meta positions on thepolyesterification reaction. To obtain such a benzene nuclei. 7 V resin, for example, a temperature of 150 to 200 2. Bis (4-,8-hydroxyethoxyphenyl) ketone. O. can be employed during the first stage of the 3. A compound as defined in claim 1 wherein reaction for from about 3 to 5 hours at atrr'ios- R1 represents a methyl radical and R2 reprepheric pressure. The resulting intermediate sents a hydrogenatom, product can then be heated at 200 C. or higher at A compound as define in claim 1 wherein a greatly reduced Pressure to 5 R1 represents a hydrogen atom and R2 represents of Hg pressure, for from about 2 to 4 hours to a methyl radicaL 5. A compound as defined in claim 1 wherein R1 and R2 each represents a methyl radical.

6. A compound as defined in claim 1 wherein R1 represents an ethyl radical and R2 represents a hydrogen atom.

sures can also be employed.

It is thus apparent that a wide variety of resins having a broad range of useful properties can be prepared by procedures similar to those set forth in the working examples above. The choice of reactants and the conditions under which the reaction takes place can be varied to suit the purpose desired.

References Cited in the file of this patent UNITED STATES PATENTS This application is a divisional application Number Name Date based upon by parent application, Serial No. 2,331,265 Coleman Oct. 5, 1943 Greenlee Apr. 15, 1952 220,535 filed on April 11, 1951. 2,592,560 

1. BIS (4-B-HYDROXYETHOXYPHENYL) KETONES HAVING THE FORMULA: 